Composition containing antioxidant



Patented June 27, E44.

NITED STATES PATENT tries 2,252,229 COMPOSITION comammc momma Sol sustains. Washington, n.'c.

No Drawing.

pplication October 14, 1940,

Serial No. 361,151 8 Claims. (Cl. 260-3985) This invention relates to antioxidantsand compositions containing the same as well as methods of producing the antioxidants and the compositions. p

Thls specification-is acontinuation in part of "application Serial No. 154,937,"filed July 21,1937,

betaine derivatives themselves as novel entities.

Still further objects include methods of producing such betaine entities as well as compositions containing the same.

Still further objectsand advantages will ap-' "pear from the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of iilustration and explanation only, and not by way The unsaturated alcohols have particularly been emphasized and illustrated above, while exemplary of the alkylamino acids, the betaines may terlals.

be mentioned. The-latter are usually considered to be in the form of inner anhydrides, but their antioxidant activity is believed to be due to a combination of elements in the molecule, including the nitrogen group, and the unsaturated and alcohols groups present in thetautomeric form of the betaines. Betaine itself is. as pointed out below, the best example of this group ofma- V The alcohols may be utilized in the form of their esters or other derivatives, such as the esters of both organic and inorganic acids,

the various phosphoric acid derivatives being particularly important, and they will be utilized for exemplification purposes below. The various of limitation, since various changes therein may be made by' those skilled in the art without departing from the scope and spirit of the present invention. 1

In explanation of the present invention it is -desirable to pointout the material disclosed in the prior specification-Serial No. 154,937 above identified. As there set forth, the antioxidants may be either chemical entities or synthesized chemical'entities built up synthetically, either from-the individual components ultimately reacted together to give 'the' complex organic 1 derivatives of desired antioxidative value, or they may be formed by synthetically utilizing natural-' ly occurring materials as a. basis for. one of the components, the synthetic antioxidants being produced directly in situ by synthesis from su'ch naturally occurring materials.

Particularly useful as antioxidants are bodies which may generally be classed together as hydroxyl containin'g"substances, including unsatucohols, or the more omplex unsaturated aicohols, such as the lipocl alcohols, including phy'tdsterol and cholesterol, the alkyl amines,

rated aliphatic alcohoigiiike'vinyl and allyl alparticularly the'alkylamino alcohols and the al- .kylamino acids, the esters of these various alcohols withorganic and inorganic acids, and the substances illustrated above, including the alkylamino acids. the-alkyiamino alcohols, the unsaturated alcohols, the lipoid alcohols, etc. may all I be utilized directly as antioxidants, using, for

example, a fraction of a percent of such antioxidant added to or' contacted with the substance to be protected against oxidative change. Thus 0.5% of the indicated material may be added to a glyceride oil or fat to protect the latter against development of rancidity. Where the antioxidants, such as the betaines, include acid groups, the latter may be esterified with alcohols of various types to produce derivatives utilizable as antioxidants,

Among the alkylamino alcohols and alkylamino acids, the derivatives containing pentavalent nitrogen in the nature of derivatives of tri-alkyl-ammonium hydroxide are particularly useful illustrated by choline, namely hydroxyethyl-tri-methyl-ammonium hydroxide, colamine, etc., while the analogous alkylamino acids illustrated by the betaines, exemplified by betaine specifically (oxy-neurine or lyclne) COOECH:.N(CHJ) 3.0K

their various homologues and derivatives may be employed.

The following specific example of one manner of the preparation of alkylamino-alkyL-phosphoric acid esters built up from their components, and utilizable asantioxidants is given:

23 parts oi phosphorus pentoxide are stirred m mic a melt of 100 parts of distearin, and after a few. minutes 54 parts of a choline salt, such as bicarbonate, are added, and the mixture stirred and kneaded until it solidifies. The resulting mixture contains the antioxidants. particularlyesters and salts of the aikylamino derivatives. 55 in the form of a choline derivative of glycerolmine'and adrenaline, or other ammonium base, or an arsonlum base may be employed. The diglycerides, such as dist'earin, may vary in character, and may be employed as such in the reaction, or diglycerides mixed with triglycerides or neutral vegetable and animal products, with the utilizatures of materials. are producfl, and they are capable of ,directusefor antioxidative purposes in manners and ways ustratedbelow.

' If desired to segregate the alkylamino-alkylphosphoric acid ester, themixture as produced above maybe treated with hot benzol, which dissolves thealkylamino-alkyl-phosphoric acid ester and leaves other derivatives, such as choline phosphate, 7 tially undissolved. The file; trate may be neutralized as by alcoholic alkali metal hydroxides, and the solution concentrated or allowed to crystallize outdirectly with cooling. Further purification may be carried out by means. of benzol, if]desired.'

i. a The examples .given above'may. be varied in many'diiferent ways-by trans'posing the order of Y the steps. for example, and permitting first the distearin and the choline derivative to react,etc. The amino-alcohol, such as the choline is desirably employed in the form of a salt, either or an inorganic or an organic acid, such as the carbon- 1 ate, bicarbonate, fatty acid salt, etc. Co1amfi1e,as noted may be substituted for choline, or other. amino-alcohols may be utilized, such as ethanolafats may be employed. Other methods of synthesizing analogous derivatives may be employed. Thus the phosphoric acid ester of distearin may first be prepared, and choline then permitted to react therewith. Or a diglyceride-phosphoric acid maybe permitted to be esterifled' with ethylene glycol or its chlorhydrin, and the resulting product or ester treated with trimethylamine.

Since choline and related compounds are widely distributed in animal and vegetable materials; such natural products containing choline may be utilized in lieu of the choline of the example given above to produce corresponding compounds di-' rectly in situ in the vegetable of animal materials,

and the resulting products employed as antioxidants. Thus hops, which contain choline, may

.be subjected to, treatment with thephosphoric acid ester ofdistearin, so that combination of the phosphoric acid ester of distearin with the choline or related compound in the natural material occurs. This is exemplary oi the production of antioxidants directly in situ in natural occurring tion of'the'latter either for admixture with additional quantities of analogous vegetable or animal materials respectively, or for addition or use with other substances as antioxidants.

The. various proteid substances may be directly subjected to treatment with any of the phosphoric acidsfbut particularly metaphosphoric acid, and

, more particularly 'by the utilization of glycerolphosphoric acids for conversion into materials utillzableas antioxidants, or such glycerol-phosphoric acid combinations thus produced may be further treated with choline or other amino-alcohols, as setforth above, for the production of still'more complex materials utilizable as antij oxidants; Any of the proteid materials, including the proteins, albumins, etc., such as casein, glue, gelatin; etc, maybe employed. For example, casein may be'treated with glycerol-phosphate as, for. example, by suspending casein in'10%. aque- ,ous alcohol, and -adding glycerol-phosphate of.

- aseaaaa I phosphoric acid containing the stearic residues bound in the molecule. By such reactions,,mix-

sodium thereto in the proportion. or 16 of the glycerol-phosphate to each gram of casein.

' Gluten of wheat or zein of corn may be similarly treated. The combinations may be heated gently to produce the desired products, and water subsequently removed as by means of strong alcojhols. The products maybe evaporated in vacuo /at low temperatures, such as 40 (3., or may be precipitated from the medium by means of alcohols.

Instead "of glycerol phosphate, the fatty acidglycerin-phosphoric acids, such as the palmityl,

. oleyl, and stearyl glycerin-phosphoric acids may be employed. For example, parts of casein are treated with-lO-part's or 50% disodium-dh stearyl-glycerin-phosphate in suspension in aqueous or alcoholic liquids, and the product dried at low temperatures, preferablyin vacuo. i Such glycerol-phosphoric acid derivatives ob! tained by direct reaction with various proteid substances, either substantiahy pure proteins andalbumins, such as casein, or natural products containing' substantial amounts of such materials, obtained in the manner set forth above, maybe further. treated with choline or other amino-alcohols to produce antioxidants.

Instead oi'producinga distearin or other diglyceride by synthetic methodsas set forth above in the specific example for the formation of the ,alkyl-amino alkyisphosphoric acid esters, a natural oil or fat, or oil or fat-containing product, may be utilized. Such natural oil or fat" may be subjected to alcoholysis to. produce adiglyceride, or mixtures containing diglycerides, may be employed in the manner set forth in the specific I example given above for reaction with phosphorus pentoxide andcholine to produce the corresponding alkylamind-alkyl-phosphoric acid esters. Alcoholysis' is well known, and, may be employed in the usual way byt'rea'ting 'an oil, .for example, with a polyhydric alcohol, heating the mixture at elevated temperatures to give the desired (11- a glycerldes.

Thus an ordinary bland oil of saturated character, and containing substantially triglycerides only, is heated with glycerol, a glycol, etc.',' glycerol being preferred in thepresent in stance. V: of a mol of glycerol may be-used to 1' mol of triglycerides, and the mixture heated, for example, for several hours at elevated tempera- -tures,as, for example, about 200? 'C. until'alcoholysis is completed. While bland oils have been specifically mentioned above. any of the edible oils may be thus treated, andinedibie oils, such as the drying oils or semi-drying oils, may

also be subjected toalcoholysis. Linseed oil, for example, may be heated with glycerol, 282 parts of linseed oil being heated with 92 parts of glycerol for 3 hours at -180". 0., desirably an inert gas like carbon dioxide gas being passed through the reaction mixture during the heat treatment. Al,-' coholysis is substantially complete at the end or that period. I Catalysts, such as calcium glycerate or glycolate may be utilized during the alcoholysis reaction. The diglycerides or mixtures containing them may then, be subjected to the steps given in the specific example above'for the" I production of thephosphoric acid esters."

An advantage of the method-ofproducing such dlglycerides by alcoholysis of an oil-is the fact that the antioxidants can be built up in the on itself in part from the-constituents of theoil.

.The entire oilmay be converted'into the die 'glyceride'andutilized for the production or the alkyl-amino-alkyl phosphoric acidestersin accordance with the specific .exan'iplegiven above, and the resulting, alkyl-amino-alkyl PhQ phoric assasso be converted only in part into a diglycerldefthe latter remaining distributed through the bulk oftriglycerlde which remains unchanged, and such diglyceride-containing oil then subjected to the production of the alkylamino-alkyl-phosphoric acid ester to produce the latter distributed through the main body of the unchanged oil, whereupon the antioxidant is produced in situ in the oil. Refined oils may particularly be treated in this way to give them antioxidant properties and resistance to development of rancidity.

Another manner of treating the oil to produce the antioxidants in situ therein is to employ oils containing some acids, such as rancid oils, or oils which have been partially hydrolyzed to produce acids therein, so that the oils or fat contain acids of the same character as those present as esters obtained i'romthe seeds 01' ienugreek, may similarly be employed, and the melasse or other sugar beet residues containing the betaine or the seeds of-fenugreek may be employed as antioxidants -utilizing the desired materials in powdered condition, or-in'suspenslon, in contact with the substances to be protected against oxidation, particularly as further pointed out-below. Instead of utilizing the betaines represented by betaine directly as an antioxidant, thebetaines may be utilized for the production or alkylamino-alkyl-phosphoric acid esters analogous to those obtaineddrom choline substituting, for

in the oils. Such acid-containing oils may then-1 be treated with any of the alcoholic bodies, such 7 as th'eunsaturated alcohols, the allrylamino alcohols, the lipoid alcohols, etc. to produce esters of the acids present in the oils with such alcohol bodies. The usual types or esteriflcation reactions are available for use in this connection. For example, a rancid oil may, have choline or Dhytosterol added thereto in the proportion of 1 mol of the free acids of the oil to 1 mol oi the alcohol, andthe resulting mixture then heated to temperatures of' about 105 C. for several hours in order to produce the esters. Esteriflcation catalysts may, of. course, beemployed it desired to accelerate the reaction, and an inert gas like nitrogen may be blown through the reaction mixture during the heating in order to remove water. Or a further procedure is to take such acid-containing oil and esterii'y'the acid present therein with an excess of polyhydric alcohol, so that the ester produced is either a mono or diester of the polyhydric alcohol. To illustrate the proportions that may be utilized for this purpose, to an acid-containing-oil there may be added glycerol in the ratio of 1 mol of glycerol to 2 mols of the acid present in the oil, followed by desteriflcation to produce a di-acyl of glycerine. This material present in the oil itself may then above, as for example, by treatment with one o! the alcohols, such as choline, or an unsaturated alcohol, or a lipoid 'alcohoL-such as phytosterol, or any of the amino-alcohols. in order to produce further more complex bodies having pronounced antioxidative activity.

' In lieu oi the alkylamino-aicohols, the alkylamino acids, as illustrated a stsine, referred to above,- may similarly be employed. ,The betaines may be directly employed asantioxidants. Be taine itself is available as a by-product from beet sugar manufacture, betaine being .iound extensively in sugar beats, and also in other vegetable products, and in animal products, such as shellfflsh. It y be readily producedsyntheticallyby oxidizing choline, andin other ways. Its ready availability in the residues frombeetsugar manufacture, such as in the so-called melasse gives a ready source for its derivation. Other natural occurring betaines, such as trlgoneiline,

example, approximately parts of betaine for the 54 parts of choline bicarbonate in the specinc example given above. Theresulting prodnot is an alkylamino-alkyl-phosphoric acid ester that can be utilized for antioxidant purposes. The melasse may be treated directly with the distearyl-phosphoric acid ester, or other phosphoric acid ester or a diglyceride to produce corresponding antioxidants.

Since the betaines are acid bodies, they may be utilized for production of esters by reaction with alcohols, particularly the unsaturated alcohols.

and also the amino-alcohols, as well as-the iipoid alcohols, like phytosterol, for the production oi esters utilizable as antioxidants.

The antioxidants including the betalnes and the alkylamino-alkyl-phosphm'ic acid esters, etc.

. may be employed for the protection or a wide variety oi materials against oxidation. They, may be added in limited proportions, such as only a fraction of a per cent to oils or tats to protect the latter against oxidation, or they may be dusted on food products to produce a dusted-on coat ing protecting the latter against development of rancidity, or undesirable ch e in the oils or fats contained in such edible p ucts. Orpackaging materials carrying the, stated antioxidants may be produced, such as paper carrying a sizing coating including the stated-synthetic antioxidants, and such packaging materials employed as a wrapper for the products to be protected against development of rancidity.

The alkylamino-allryl phosphoric acid esters :prcduced as illustrated in the specific example given above may be formulated as follows, where glycerol is the polyhydric alcohol used (as in the case of the distearin of that example):

wherein R is the slycerol'residue, I! and ,R: are. the stearic acid residues. (.COCi-IHss). R: is the hosphoric acid residue (0.20.011), and R4 is the choline residue (CH2.-CH2.N(OH) ((33%)..

R1 and B: may be any monobasic carboxylic acid. (acyl) residues, saturated or unsaturated, the

.higher fatty acids like stearic, palmltic, and

ol eic being preferred, and while-in the example Bi and R: are the same mi groups, they maybe the same or diflerent. While R: is thephos- Rs being the glycol erols, the. glycols) such as ethylene and propylene glycol, the polyglyools, the ethers of the glycerols or.polyglycerols,-mannitol,.etc. The glycol derivatives are particularly important and lead tonovel antioxidant materials, Thus if inlieu of the distearin oi the-specific example, there is. used about'50'parts oi the mono-stearic ester of ethylene glycol, there is formed the stearyl glycolphosphoric acid ester of choline, representative .0! compounds formulated as aliphatic and aromatic with the latter as aryl groups,- either with or without'side chains.

Further, if in producing the desiredv antioxi dants in situ from natural glycerides, such as the edible oils, wherein asexplained above, al-

coholysis is used to form in the oil a glyceride having a free hydroxyl (as, for example, distearin), a polyhydric alcohol different irom glycerol isemployed, as torexample, a glycol, mixed polyhydric alcohol estersare produced leading to complex mixtures of'the ultimate aikylaminoalkyl comp unds, which mixtures, however, without segregation can be utilized for antioxidant It now a naturaioil-containing proteid ma rial including any of theoil-containing seeds," nuts and fruits, such ascottonseed, sesame seed,-

etc., etc. is subjected to pressing to liberate the oil, but without segregation of the oil from the protein material or the'cell walls, etc., the mixture is subjected first to alcoholysis to produce a polyhydric alcohol ester having a free hydroxyl group," and such mixture is treated with phos-' phorus pentoxide as in the given example, rolloweaby the addition of choline, for example, antioxidants are obtained containing the phosactor should be chosen. roinquids the antioxidants may-be dissolvedor suspended therein or coated on containers. For solids, theantioxidants may be admixed with the product, or

dusted thereon, or-applied as a coating-or sizing on the container or the material from which the container is-made, or'to wrapping materials.

It shouldbe kept in mind that when the alkylaminoalkyl phosphoric acid esters or related materials are produced in situ, particularly by the treatment of natural materials, that individual compounds are not generally obtained,but complex mixtures of closely related derivatives are produced. However, such complex mixtures of derivatives are all utilizable as antioxidants withv out segregation of individual components or comphoric acid esters oi the protein, as well as the glyceride residues. t Unless separation is used to segregate the individual components, the synthetic methods of producing antioxidants asherein set iorthlead to complex mixtu'res,= which mixtures may be used directly as antioxidants without sesrega tion or particular components therefrom, unless I the latter are individually desired. Thus where the alkylamino-alkyl-phosphoric acid esters are produced, other derivatives are formed at the same time, ior examplefiamino-alkyl phosphoric acid esters. The latter may be left in the reaction mixture for their own antioxidative ei- V iects.

In'-use,-these antioxidants may be contacted .in anydesired way with the substances to be protected. Oils and fats. oil and fat containing products, solids and liquids oi -various types,

edible and inedible'products, meats, flesh products,,hydrocarbon oils and waxes, coflee, paint oils, w s and resins, etc. are exemplary oi prodthat can be treated i'orprotection. For

ucts edible substances, antioxidantsof inoe mus char.-

protect the latter; preferably in this instance the same blood recovered from the animal whose meat is to be protected isemployed. Or synthetic esters of the lipoid alcohols can be used. Thus phytosterol may be converted into in organic or' organic esters, as with any 01 the phosphoric acids to produce an ester having antioxidant value.. Such synthetic esters may be produced in situ by treating substances containing such iipoid alcohols or their'compounds, as phytosterol, with an acid such as phosphoric acid, to produce the ester in situ. Where the acid used is polybasic as in theme oi phosphoric acid, another 0! the hydroxyl groups of the acid can be esterifled as with glycerol. while still, if desired, retaining acid properties in the molecule. Thus glycerophosphoric acids o phytos terol etc. may be produced. All such derivatives may be used as antioxidants in the manner set iorthabove. I

Inaccordance with the present invention in order to produce antioxidant derivatives of the betaines which havea greater compatibility for or solubility in the glycerides per se, there are employed-the iatty acid derivatives or the be taines. The betaines employed may be any of the available betaines includingbetaine-per se, or other natural occurring betaines such as trigonelline, obtained from the seeds of fenugreek, or syn- I thetically produced betaines such as are obtained by oxidizing choline, may be employed, or melasse, the residues from beet sugarmanufacture, containing substantial quantities of betaine may be employed directly without segregation of the betaine therefrom.

The betaines are desirably converted into fatty acid derivatives for use in accordance with the present invention, particularly in connection with glycerides, either animal or vegetable, liquid or solid, fat oils, etc., as well as in connection with duced from the fats or oils 'themselvesby saponiflcation. As exemplary ofthe glyceride oils whichmay be employed as a source of the butterfat yielding butyric, caproic,

fatty acids utilized in producing the betaine derivatives employed in accordance with the present invention, there may be mentioned almond oil yielding oleic, pahnitic, linoleic, etc. acids, capric, palmitic, stearic, oleic, etc. acids, cacao butter giving palmitic, oleic, stearic, myristic, etc. acids,

castor oil giving ricinoleic, stearic, oleic acids,

etc., cocoanut oil yielding caproic, caprylic, caprlc, lauric, etc. acids, codliver oilgiving oleic, myristic, palmitic, stearic, etc. acids, cottonseed oil giving oleic, stearic, palmitic, linoleic, etc. acids, hemp oil giving isolinolenic, oleic, etc. acids, lard giving stearic, palmitic, oleic, linoleic, etc. acids, linseed oil yielding linoleic, linolenic, oleic, palmitic, myristic, etc. acids, maize oil giving arachidic, 'stearic, palmitic, oleic, etc. acids,

menhaden oil giving palmitic, myristic, oleic,

stearic, and other unsaturated acids. etc., .mus-

tard oil yielding erucic, arachidic, stearic, oleic,;

oleic, oleic, arachidic, etc. acids, palm oil giving palmitic, lauric. oleic, etc. acids, peanut oil yielding arachidic, linoleic, hypogoeic, palmitic, etc.

taine derivatives. The same considerations apply to the utilization of inorganic acids or organic acids other than the fatty acids in the production of mixed derivatives of the betaine with the fatty acid and inorganic acids or organic acids other than the fatty acids may be employed in such complexes where they are utilized for edible purposes, such other acids being chosen with respect to their availability for use in the human or other animal bodies; whereas different types of acids may be employed if the product is not to be used for edible purposes.

Rancid oils containing free fatty acids may desirably be-employed by treatment with a betaine of, any desired character to produce the derivative of betaine and fatty acid directly in situ inthe glyceride oil itself and to improve its qualities not only by eliminating free fatty acids contained acids, poppy oil giving linoleic, isolinolenia'.

palmitic, stearic, etc. acids, rape oil yielding erucic, arachidic, stearic acids, etc., sperm oil giving oleic, palmitic, etc. acids, tallow yielding stearic, palmltic, oleic acid complexes, and whale oil yielding linoleic, isolinolenic, etc. acids. The complex acid mixtures obtained from any of the above oils may be utilized, or the individual acids or any desired mixtures thereof may be employed in producing the betaine derivatives desirably employed in accordance with the present invention.

In producing the desired derivatives for utiliza- I tion in accordance with the present invention, any of the fatty acids as set forth above, or mix tures thereof may be utilized with a betaine but in the glyceride, but also by giving antioxidant properties to the composition.

As illustrative of inorganic acids that may be utilized in producing mixed complexes and derivatives as set forth above, reference may be made to phosphoric, sulphuric, nitric, and other inorganic acids, while organic acids other than the fatty acids that may be employed include any of the aliphatic, aromatic and heterocyclic acids such as benzoic, phthalic, succlnic, tartaric, lactic. naphthenic, etc. acids.

The betaine derivatives are readily produced by heating the betaine with the desired fatty acid or by heating melasse with the desired fatty acid at relatively low temperatures generally not exceeding the boiling point of water and usually substantially lower. temperatures of 60 to 70 C.

desirably being employed for this purpose However, the maximum temperatures employed should be below those at which the components are subiected to undesirable decomposition. It is only necessary to mix the betaine or melasse containingmaterial with the desired fatty acids or fatty acid and other acids, inorganic or organic, and heat the mixture together to produce the desired derivatives. The heat treatment may .be carried out in the presence of a solvent or vehicle including water and organic solvents such asalcohol, acetone, light hydrocarbon distillates like petroleum ethers, etc., or the oils may be used as a medium in which the reactionis carried out, the

Where the betaine derivatives are employed in connection with glyceride or other oils employed for edible purposes, then desirably the derivatives of betaine are produced with acids that are wholesome and available for edible purposes. Thus the cottonseed oil fatty acid complexes may desirably be utilized in producing the derivatives'of betaine such as betaine itself and the derivative of betaine with the cottonseed oil fatty acid may be employed in connection with an edible glyceride oil such as cottonseed oil, maize oil, cocoanut oil, peanut oil, etc., in order to yield antioxidant properties therein.

Where, however, the ultimate product is employed for non-edible purposes as in connection solvent or vehicle emp yed being either a solvent for'bne or more of the ingredients which are undergoing reaction or both materials may be suspended in a medium if desired. Where inorganic acids are employed such as phosphoric, water solutions of the acid may be employed or water solutions of water-soluble organic acids may be employed for heat treatment with the betaine to produce the desired derivatives. Many of the Thus, in the preparation of an oleic acid derivative of betaine, 82 parts by weight of oleic acid may be heated to 80 C. and 18 parts of betaine added thereto. The mixture is heated at a.temperature between 60 and 70 (1. for approximately 2 hours to produce the desired oleic acid derivative of betaine. Theresulting complex may be utilized as such for addition to slycerides and parts of'betaine incorporated therewith; and the other products as an antioxidant, small quantities thereof being employed. as for example. 0.5%. I In the production of a palmitic acid derivative of melasse, the following may-be carried out. '15 a parts by weight of palmitic acid are heated to 70 C. and 25 parts by weight of melasse incorporated therewith, the heat-treatment being continued for 1 3 hours andthe resulting product being available for/use without ,as,set forth above.

purification, as an antioxidant In the production of a mixed fatty acid inor-p panic acid derivative of betaine, the followinz procedure may be employed. 40 parts of oleic acid are heated to 70' C. until molten, and 20 Accordingly, fatty id derivatives of the be- .taines may be produced in accordance with the present invention and utilizedeither as such 'or as mixed fatty acid esters or as-misedderivatives of betaines with fatty acids and inorganic acim or organic acids other than fatty acids, asantioxidants in the protection of various types of oils. fats and similar-materials subject. to oxidative deterioratiom The glycerlde oils, 'orother oils 7 may be contacted with a small percent of the antioxidant betaine" derivative. the fatty acid betaine derivative into the fat or oil for protective purposes. Glycerides per ie need not be treated means ofalcohol may be emassasi'ao f alone, but'glyceride similarly be es of the betainea. i

Having thus set-forth my invention, I y. Y i. A composition containing -a"glyceridesubiect to oxidative deterioration, and a fattyiacid chemically combined with a betaine as an antioxidalit. v 2. A composition containing a glyceriiie taining substance subject to oxidative deteriora-' 'tion and a higher fatty acid chemicallyicoriibined with a betaineas'anantioxidant.

3; A composition comprising a glyceride containing substance subject to' oxidative deterioration and mixed higher fatty acids chemically -'combined with a betaine, as an antioxidant.

4.A composition comprising aQglyceride-containing' substance subiect to o ridative deteriora- 8. A composition comprising 35 derivatives enabling ready incorporation of the.

tion and a betaine chemicallycombined with-.a

higher fatty acid and an inorganic acid, as an antioxidant; i 5. A composition comprising a glyceride containing substancesubiect to-oxidative deterioration and'a betaine chemically combined with a saidi'atty acid,'as anantioxidant. A Y

- 65A composition comprisinra glyceride bontaining substance subiect to oxidstive deterioration and a fatty acid chemically combined with the betaine in'melasse, aslaniantioxidant, I

fatty acid andof an organic acid diiferent froni 1. a composition comprising a .glyceride oiitaining substance subject to oxidative deterio -a tion and cottonseed oil acids chemically combined withbetainmasanantioxidant.

a slyceride and a higher fatty acid chemically combined with a betaine produced in situ from acids of the glyceride as an antioxidant for the glyceride. Y

801i SHAPPIRIO.

containing compositions may protfcted by the utilization of the fatty acid derivat v 

